CN102416345A - Mixed crystal material containing EUO zeolite and preparation method thereof - Google Patents

Mixed crystal material containing EUO zeolite and preparation method thereof Download PDF

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CN102416345A
CN102416345A CN2010102928863A CN201010292886A CN102416345A CN 102416345 A CN102416345 A CN 102416345A CN 2010102928863 A CN2010102928863 A CN 2010102928863A CN 201010292886 A CN201010292886 A CN 201010292886A CN 102416345 A CN102416345 A CN 102416345A
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mixed crystal
crystal material
molecular sieve
euo
quartzy
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高俊魁
钟进
吴巍
周震寰
王志强
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention provides an EUO/alpha quartz mixed crystal material. The characteristic peak height of alpha quartz at 26.6 degrees in the mixed crystal material is 0.4-5.0 times that of the EUO molecular sieve. The synthesis method of the mixed crystal material comprises the steps of mixing a silicon source, an aluminium source, alkali, a template agent and water to prepare a reaction solution and crystallizing the prepared reaction solution for 6-50 hours under the temperature of 160-200 DEG C and self-generated pressure of the system, wherein the mole ratio of R to Na2O to Al2O3 to SiO2 to H2O is (0.1-0.4): (0.1-0.3): (0.003-0.1): 1: (10-200); and R is the template agent for preparing the EUO molecular sieve. The mixed crystal material provided by the invention is used as the catalyst for xylene isomerisation and has lower aromatic hydrocarbon loss ratio and higher thermodynamic equilibrium approach.

Description

A kind of mixed crystal material that contains the EUO zeolite and preparation method thereof
Technical field
The present invention is a kind of mixed crystal material and preparation method thereof, specifically, is quartzy mixed crystal material of a kind of EuO/ α and preparation method thereof.
Background technology
Molecular sieve is a kind of functional material with unique texture and character, has been widely used in fields such as petrochemical industry, fine chemistry industry, environmental protection.The EUO molecular sieve has one-dimensional tunnel structure, and its aperture is 0.41 * 0.57 nanometer, these one-dimensional channels also have the degree of depth be 0.81 nanometer, diameter be 0.68 * 0.58 nanometer side pocket (Zeolite, 1988,8:74).Patents such as USP4537754, USP6514479, CN99126910.1, CN98124082.8, CN99104853.9, CN99127713.9 disclose the synthesis progress of EUO type molecular sieve and in the application in aromatic hydrocarbons field.But when being used for xylene isomerization reaction in view of EUO type molecular sieve, the shortcoming that side reaction is bigger becomes problem demanding prompt solution to its modification with the selectivity that improves its xylene isomerization reaction.
US6342200B1 discloses a kind of synthetic method of the EUO of preparation type molecular sieve, this method adopt silica alumina ratio less than the molecular sieve of other type of 200 as crystal seed, synthesize composite molecular screen.
CN1772611A discloses a kind of composite molecular sieve in ten-element cyclic structure and synthetic method thereof, and synthetic composite molecular screen comprises ZSM-22/SAPO-11, ZSM-23/SAPO-11, ZSM-5/SAPO-11, EU-1/SAPO-11, NU-87/SAPO-11 composite molecular screen.This method will have the molecular sieve of ten-ring structure and put into the raw material that synthesizes SAPO-11, carry out crystallization according to the condition of synthetic SAPO-11, obtain composite molecular screen.Said composite molecular screen is used for the normal alkane isomerization reaction, like lubricating oil dewaxing or diesel oil pour point depression.
Reported to adopt in Industrial Catalysis 2008,10 (16) and preset the synthetic EU-1/MOR composite molecular screen of crystal seed method.CN03148301.1 discloses to adopt and has preset the synthetic ZSM-5/ modenite mixed crystal material of crystal seed method.CN200410000960.4 discloses to adopt and has preset the crystal seed method and synthesize the mordenite/beta zeolite mixed crystal material.CN200410000959.1 discloses to adopt and has preset the crystal seed method and synthesize ZSM-5/ β zeolite mixed crystal material.
(Micro Mes Mater such as Karlsson; 1999; 27,181-192), synthesized MFI/MCM-41 type composite molecular screen with six alkyl trimethyl ammonium bromides and TTAB double template system; This method is through ratio and the crystallization temperature of template used dose of the synthetic MFI/MCM-41 of control, controls the relative amount of MFI and MCM-41 molecular sieve in the composite molecular screen.
Summary of the invention
The purpose of this invention is to provide the quartzy mixed crystal material of a kind of EUO/ α, this mixed crystal material is used for the catalyst of xylene isomerization reaction, has lower aromatic hydrocarbons loss late and the higher approaching value of thermodynamical equilibrium.
The quartzy mixed crystal material of EUO/ α provided by the invention, this mixed crystal material are positioned at 0.4～5.0 times of characteristic main peak height that 26.6 ° the quartzy characteristic main peak height of α is the EUO molecular sieve.
The quartzy mixed crystal material of EUO/ α provided by the invention because it is quartzy to contain an amount of α, makes mixed crystal material than pure EUO molecular sieve, has the better dimethylbenzene isomerization performance.
Description of drawings
Fig. 1 is the XRD figure of the quartzy mixed crystal material of EU-1/ α of an examples preparation of the present invention.
Fig. 2 is the XRD figure of the quartzy mixed crystal material of EU-1/ α of another examples preparation of the present invention.
Fig. 3 is the XRD figure of EU-1 molecular sieve.
The specific embodiment
The quartzy mixed crystal material of EUO/ α provided by the invention is to contain the quartzy EUO zeolite of α, and the quartzy content of EUO and α is represented by the relative altitude of characteristic main peak in its XRD figure in the mixed crystal material.Preferably, be positioned at 0.8～4.0 times of characteristic main peak height that 26.6 ° the quartzy characteristic main peak height of α is the EUO molecular sieve.
The preferred EU-1 molecular sieve of described EUO molecular sieve, its characteristic main peak is positioned at 20.5 °.
The quartzy mixed crystal material of EUO/ α provided by the invention is in synthetic EUO zeolite process, makes generation α quartzy through reducing the template consumption with the shortening crystallization time.
Specifically, the preparation method of the quartzy mixed crystal material of EUO/ α provided by the invention comprises silicon source, aluminium source, alkali, template and water are mixed and made into reaction solution that wherein each material molar ratio is: 0.1～0.4R: 0.1～0.3Na 2O: 0.003～0.1Al 2O 3: SiO 2: 10～200H 2O, wherein R is the template of preparation EUO molecular sieve, with the reaction solution of preparation crystallization 6～50 hours under 160～200 ℃ of conditions with the system self-generated pressure.
In the described reaction solution, each material molar ratio is preferably: 0.1～0.3R: 0.1～0.3Na 2O: 0.003～0.1Al 2O 3: SiO 2: 10～160H 2O.
Described template is selected from benzhydryl dimethyl ammonium or alkylation polymethylene α-ω di-ammonium salts; Oneself two ammoniums
Figure BSA00000284800800021
of described alkylation polymethylene α-preferred trimethyl dibromo of ω di-ammonium salts also can be used the mixture of trimethylammonium and dibromo-hexane, generate oneself two ammoniums of trimethyl dibromo through reaction in-situ.
The described silicon of the inventive method source is selected from amorphous silica, Ludox, ethyl orthosilicate, positive silicic acid propyl ester or butyl silicate; The aluminium source is selected from sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum alkoxide, aluminium oxide, alumine hydroxide colloid, boehmite or boehmite.Described silicon source and aluminium source are selected from unformed silica-alumina simultaneously.
The characteristics of the inventive method are that sodium-silicon-rate is lower, and the template consumption is lower, and crystallization time is shorter, are preferably 10～48 hours.
Material is through filtering after the crystallization, and the gained solids promptly gets the quartzy mixed crystal material of EUO/ α provided by the invention through washing, drying, roasting.Described baking temperature is 110～120 ℃, preferred 2～12 hours of time, and sintering temperature is 500～600 ℃, preferred 2～12 hours of time.
The quartzy mixed crystal material of EUO/ α provided by the invention is applicable to C 8The isomerization reaction of aromatic hydrocarbons, the temperature of isomerization reaction are 340～420 ℃, and pressure is 0.4～1.0MPa, and the liquid quality air speed is 1.0～6.0 hours -1, hydrogen/hydrocarbon mol ratio is 1～15.
Pass through instance further explain the present invention below, but the present invention is not limited to this.
In the instance, the crystalline phase of mixed crystal material is detected by Siemens D5005 type X-ray diffractometer, and experiment condition is: x-ray source CuK α; 0.154056 nanometer, 30 kilovolts of tube voltages, 20 milliamperes of tube currents; Filter plate is Ni, and sweep speed is 4 °/minute, 0.02 ° of step-length.
Instance 1
(1) preparation mixed crystal material
With 40g (SiO 2Content is 29 quality %) Ludox add in the 41.19g water, add sodium aluminate (Al after the stirring respectively 2O 3Content 45 quality %, Na 2O content 33 quality %) oneself two ammoniums (purity 97 quality %) 21.65g of 2.19g, NaOH 0.61g, trimethyl dibromo, material molar ratio is following:
0.3R∶0.1Na 2O∶0.1Al 2O 3∶SiO 2∶20H 2O
Wherein R is oneself two ammoniums of trimethyl dibromo; Stir; In 200 ℃ of crystallization 30 hours, be cooled to 25 ℃, through filtration under diminished pressure, the solid matter with deionized water washing that obtains; Obtained the quartzy mixed crystal material of EU-1/ α in 10 hours in 6 hours, 550 ℃ roastings of 110 ℃ of dryings then, its XRD figure spectrum is seen Fig. 1.Fig. 1 shows that this material has EU-1 crystalline phase and the quartzy characteristic peak of α, and the quartzy XRD characteristic main peak (26.6 °) of its α highly is 0.9 times of EU-1 molecular sieve characteristic main peak height (20.5 °).
(2) preparation Hydrogen mixed crystal material
Get the quartzy mixed crystal material of EU-1/ α of 5g (1) one step process preparation, with 20ml concentration be that the aqueous ammonium chloride solution of 5.0 quality % carried out ion-exchange 2 hours under 95 ℃, the condition of continuous stirring, press the similarity condition repeated exchanged more once.Mixed crystal material after the ion-exchange was made Hydrogen mixed crystal material A in 4 hours in 6 hours, 550 ℃ roastings of 120 ℃ of dryings, and compressing tablet is broken into 0.425～0.850 millimeter granule again.
Instance 2
With 40g (SiO 2Content 29 quality %) Ludox adds in the 110.79g water, adds sodium aluminate (Al after the stirring respectively 2O 3Content 45 quality %, Na 2O content 33 quality %) 0.44g, NaOH 4.45g, oneself two ammoniums (purity 97 quality %) 7.21g of trimethyl dibromo, material molar ratio is following:
0.1R∶0.3Na 2O∶0.01Al 2O 3∶SiO 2∶40H 2O
Wherein R is oneself two ammoniums of trimethyl dibromo; Stir; In 180 ℃ of crystallization 48 hours, be cooled to 25 ℃, through filtration under diminished pressure, the solid matter with deionized water washing that obtains; Obtained the quartzy mixed crystal material of EU-1/ α in 10 hours in 6 hours, 550 ℃ roastings of 110 ℃ of dryings then, its XRD figure spectrum is seen Fig. 2.Fig. 2 shows that this material has EU-1 crystalline phase and the quartzy characteristic peak of α, and the quartzy XRD characteristic main peak (26.6 °) of its α highly is 3.2 times of EU-1 molecular sieve characteristic main peak (20.5 °) height.
Get the quartzy mixed crystal material of EU-1/ α of 5g method for preparing, the method that goes on foot by instance 1 (2) prepares Hydrogen mixed crystal material B.
Instance 3
11.6g amorphous silica (white carbon) is joined in the 174g water, add sodium aluminate (Al after the stirring respectively 2O 3Content 45 quality %, Na 2O content 33 quality %) 1.46g, NaOH 2.10g, oneself two ammoniums (purity 97 quality %) 13.99g of trimethyl dibromo, material molar ratio is following:
0.2R∶0.167Na 2O∶0.033Al 2O 3∶SiO 2∶50H 2O
Wherein R is oneself two ammoniums of trimethyl dibromo; Stir,, be cooled to 25 ℃ in 200 ℃ of crystallization 40 hours; Through filtration under diminished pressure, the solid matter with deionized water washing that obtains; Obtained the quartzy mixed crystal material of EU-1/ α in 10 hours in 4 hours, 500 ℃ roastings of 120 ℃ of dryings then, identify that through XRD it has EU-1 molecular sieve crystalline phase and the quartzy characteristic peak of α, the height of the quartzy XRD characteristic main peak of its α (26.6 °) is 1.8 times of EU-1 molecular sieve characteristic main peak (20.5 °) height.
Get the quartzy mixed crystal material of EU-1/ α of 5g method for preparing, the method that goes on foot by instance 1 (2) prepares Hydrogen mixed crystal material C.
Instance 4
11.6g amorphous silica (white carbon) is added in the 556.70g water, add boehmite (Al after the stirring respectively 2O 3Content 76 quality %) 0.13g, NaOH 3.09g, oneself two ammoniums (purity 97 quality %) 21.65g of trimethyl dibromo, material molar ratio is following:
0.3R∶0.2Na 2O∶0.005Al 2O 3∶SiO 2∶160H 2O
Wherein R is oneself two ammoniums of trimethyl dibromo; Stir,, be cooled to 25 ℃ in 200 ℃ of crystallization 24 hours; Through filtration under diminished pressure, the solid matter with deionized water washing that obtains; Obtained the quartzy mixed crystal material of EU-1/ α in 2 hours in 4 hours, 600 ℃ roastings of 120 ℃ of dryings then, identify that through XRD it has EU-1 molecular sieve crystalline phase and the quartzy characteristic peak of α, the quartzy XRD characteristic main peak of its α (26.6 °) highly is 1.2 times of EU-1 molecular sieve characteristic main peak (20.5 °) height.
Get the quartzy mixed crystal material of EU-1/ α of 5g method for preparing, the method that goes on foot by instance 1 (2) prepares Hydrogen mixed crystal material D.
Instance 5
11.6g amorphous silica (white carbon) is joined in the 104.4g water, add sodium aluminate (Al after the stirring respectively 2O 3Content 45 quality %, Na 2O content 33 quality %) 0.88g, NaOH 2.72g, oneself two ammoniums (purity 97 quality %) 13.99g of trimethyl dibromo, material molar ratio is following:
0.2R∶0.2Na 2O∶0.02Al 2O 3∶SiO 2∶30H 2O
Wherein R is oneself two ammoniums of trimethyl dibromo; Stir,, be cooled to 25 ℃ in 200 ℃ of crystallization 12 hours; Through filtration under diminished pressure, the solid matter with deionized water washing that obtains; So obtained the quartzy mixed crystal material of EU-1/ α in 10 hours in 4 hours, 500 ℃ roastings of 120 ℃ of dryings, identify that through XRD it has EU-1 molecular sieve crystalline phase and the quartzy characteristic peak of α, the height of the quartzy XRD characteristic main peak of its α (26.6 °) is 2.2 times of EU-1 molecular sieve characteristic main peak (20.5 °) height.
Get the quartzy mixed crystal material of EU-1/ α of 5g method for preparing, the method that goes on foot by instance 1 (2) prepares Hydrogen mixed crystal material E.
Instance 6
With 40g (SiO 2Content 29 quality %) Ludox adds in the 145.6g water, adds sodium aluminate (Al after the stirring respectively 2O 3Content 45 quality %, Na 2O content 33 quality %) 0.55g, NaOH 2.86g, oneself two ammoniums (purity 97 quality %) 21.63g of trimethyl dibromo, material molar ratio is following:
0.3R∶0.2Na 2O∶0.0125Al 2O 3∶SiO 2∶50H 2O
Wherein R is oneself two ammoniums of trimethyl dibromo; Stir,, be cooled to 25 ℃ in 180 ℃ of crystallization 48 hours; Through filtration under diminished pressure, the solid matter with deionized water washing that obtains; Obtained the quartzy mixed crystal material of EU-1/ α in 10 hours in 6 hours, 550 ℃ roastings of 110 ℃ of dryings then, identify that through XRD it has EU-1 molecular sieve crystalline phase and the quartzy characteristic peak of α, the height of the quartzy XRD characteristic main peak of its α (26.6 °) is 1.6 times of EU-1 molecular sieve characteristic main peak (20.5 °) height.
Get the quartzy mixed crystal material of EU-1/ α of 5g method for preparing, the method that goes on foot by instance 1 (2) prepares Hydrogen mixed crystal material F.
Comparative Examples 1
11.6g amorphous silica (white carbon) is joined in the 162.38g water, add sodium aluminate (Al after the stirring respectively 2O 3Content 45 quality %, Na 2O content 33 quality %) 1.46g, NaOH 2.10g, oneself two ammoniums (purity 97 quality %) 23.30g of trimethyl dibromo, material molar ratio is following:
0.333R∶0.167Na 2O∶0.033Al 2O 3∶SiO 2∶46.67H 2O
Wherein R is oneself two ammoniums of trimethyl dibromo, stirs, in 200 ℃ of crystallization 100 hours; Be cooled to 25 ℃; Through filtration under diminished pressure, the solid matter with deionized water washing that obtains, obtained the EU-1 molecular sieve in 10 hours in 6 hours, 550 ℃ roastings of 110 ℃ of dryings then, the XRD figure spectrum is seen Fig. 3.Fig. 3 shows that this material has EU-1 molecular sieve crystalline phase.
Get the above-mentioned EU-1 molecular sieve of 5g, the method that goes on foot by instance 1 (2) prepares Hydrogen EU-1 molecular sieve H.
Comparative Examples 2
With 40g (SiO 2Content 29 quality %) Ludox adds in the 145.6g water, adds sodium aluminate (Al after the stirring respectively 2O 3Content 45 quality %, Na 2O content 33 quality %) 0.55g, NaOH 4.41g, oneself two ammoniums (purity 97 quality %) 28.84g of trimethyl dibromo, material molar ratio is following:
0.4R∶0.3Na 2O∶0.0125Al 2O 3∶SiO 2∶50H 2O
Wherein R is oneself two ammoniums of trimethyl dibromo; Stir,, be cooled to 25 ℃ in 200 ℃ of crystallization 60 hours; Through filtration under diminished pressure, the solid matter with deionized water washing that obtains; Obtained the quartzy mixed crystal material of EU-1/ α in 10 hours in 6 hours, 550 ℃ roastings of 110 ℃ of dryings then, bright this material of XRD figure stave has EU-1 molecular sieve crystalline phase and the quartzy characteristic peak of α, and the height of the quartzy XRD characteristic main peak of its α (26.6 °) is 0.2 times of EU-1 molecular sieve characteristic main peak (20.5 °) height.
Get the quartzy mixed crystal material of EU-1/ α of 5g method for preparing, the method that goes on foot by instance 1 (2) prepares Hydrogen mixed crystal material M.
Instance 7～14
Following instance is estimated the xylene isomerization performance of mixed crystal material.
On micro-reactor; Load 0.6g Hydrogen mixed crystal granular materials respectively; Under the condition of 370 ℃ of reaction temperatures, pressure 0.6MPa, liquid quality air speed 3.0, hydrogen/hydrocarbon mol ratio 5, the employing meta-xylene is a probe, investigates the xylene isomerization reaction performance of filling material.Reaction raw materials and product are analyzed with HP7890 gas chromatograph (FID, DM-WAX chromatographic column), analysis condition: 250 ℃ of injector temperatures, 300 ℃ of detector temperatures, 100 ℃ of column temperatures.Reaction result is seen table 1, and table 1 shows that the quartzy mixed crystal material of the EU-1/ α of the present invention's preparation has lower aromatic hydrocarbons loss late and the bigger approaching value of paraxylene thermodynamical equilibrium than pure EU-1 molecular sieve.
The paraxylene thermodynamical equilibrium is expressed as near value (PATE):
PATE＝{[(PX) y-(PX) r]/[(PX) e-(PX) r]}×100％
In the formula, PX=(PX/ ∑ X) * 100%
∑ X is xylenes summation (OX+PX+MX); Subscript r, y, e represent raw material, product and equilibrium liquid respectively, in the 650K equilibrium liquid (PX) eBe about 23.7 quality %.
Table 1
Figure BSA00000284800800071

Claims (11)

1. the quartzy mixed crystal material of an EUO/ α, this mixed crystal material are positioned at 0.4～5.0 times of characteristic main peak height that 26.6 ° the quartzy characteristic main peak height of α is the EUO molecular sieve.
2. according to the described mixed crystal material of claim 1, the quartzy characteristic main peak height of α that it is characterized in that being positioned at 26.6 ° is 0.8～4.0 times of characteristic main peak height of EUO molecular sieve.
3. according to claim 1 or 2 described mixed crystal materials, it is characterized in that described EUO molecular sieve is the EU-1 molecular sieve.
4. according to the described mixed crystal material of claim 3, it is characterized in that the characteristic main peak of EU-1 molecular sieve is positioned at 20.5 °.
5. the preparation method of the quartzy mixed crystal material of EUO/ α comprises silicon source, aluminium source, alkali, template and water are mixed and made into reaction solution that wherein each material molar ratio is: 0.1～0.4R: 0.1～0.3Na 2O: 0.003～0.1Al 2O 3: SiO 2: 10～200H 2O, wherein R is the template of preparation EUO molecular sieve, with the reaction solution of preparation crystallization 6～50 hours under 160～200 ℃ of conditions with the system self-generated pressure.
6. according to the described method of claim 1, it is characterized in that each material molar ratio is in the described reaction solution: 0.1～0.3R: 0.1～0.3Na 2O: 0.003～0.1Al 2O 3: SiO 2: 10～160H 2O.
7. according to the described method of claim 5, it is characterized in that described template is selected from benzhydryl dimethyl ammonium or alkylation polymethylene α-ω di-ammonium salts.
8. according to the described method of claim 5, it is characterized in that described alkylation polymethylene α-ω di-ammonium salts is oneself two ammoniums of trimethyl dibromo.
9. according to the described method of claim 5, it is characterized in that described silicon source is selected from amorphous silica, Ludox, ethyl orthosilicate, positive silicic acid propyl ester or butyl silicate; The aluminium source is selected from sodium aluminate, aluminum sulfate, aluminum nitrate, aluminum alkoxide, aluminium oxide, alumine hydroxide colloid, boehmite or boehmite.
10. according to the described method of claim 5, it is characterized in that described silicon source and aluminium source are selected from unformed silica-alumina simultaneously.
11., it is characterized in that crystallization time is 10～48 hours according to the described method of claim 5.
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
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CN101722020A (en) * 2008-10-15 2010-06-09 中国石油天然气股份有限公司 Eutectic zeolite catalyst containing EUO structure and preparation method and application thereof

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CN101554592A (en) * 2008-04-08 2009-10-14 中国科学院大连化学物理研究所 Preparation method of high silica alumina ratio MCM-22 molecular sieve catalyst
CN101722020A (en) * 2008-10-15 2010-06-09 中国石油天然气股份有限公司 Eutectic zeolite catalyst containing EUO structure and preparation method and application thereof
CN101530812A (en) * 2009-04-15 2009-09-16 中国科学院大连化学物理研究所 ITQ-13 molecular sieve catalyst and method for preparing same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105080478A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Method for separating low octane value components from mixed hydrocarbons

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